DE1938486A1 - Catalysts for the polymerization of olefinic hydrocarbons - Google Patents

Description

■■! '- 4361-2

Sumitomo Chemical Company, Ltd., 15 5-Chome, Kitahama Higashi-Ku, Osaka / Japan

Catalysts for the polymerization of olefinic hydrocarbons

The present invention relates to new catalysts for the polymerization of olefin hydrocarbons, which are the main components contain new vanadium compound and an organoaluminum compound. In particular, the present invention on catalysts for the polymerization of olef ^ hydrocarbons, with "which amorphous o ^ efin copolymers are produced into which a polyene compound is effectively polymerized.

There are already various polymerization catalysts for the production of amorphous olefin copolymers has been proposed. Specifically effective are Ziegler catalysts and among these have the combinations of a vanadium compound with an organoaluminum compound proved to be extremely useful. To the representative representatives

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this type of vanadium compounds include the halogen compounds, azoxy compounds, the acetylacetonates and the like, and their technical importance lies in their use for the production of amorphous copolymers.

In the production of sulfur-vulcanizable, rubber-like compounds by means of mixed polymers sation of.Ethylen with oC-olefins and diene compounds or other polyene compounds using catalysts of the so-called Ziegler-Nattä type the diene compounds or the other polyene compounds, especially the conjugated diene compounds, generally have a retarding effect the polymerization by means of the Ziegler-Natta catalysts the end. In Italian patent specification 664 769 (or British patent specification 983 4Jf) a polymerization catalyst is described which using an organoaluminum compound is ,, into which a stereometrically bulky group has been introduced, so that the interpolymerization of conjugated diolefins to be able to carry out easily.

Catalysts of the Ziegler-Natta type which use vanadium compounds containing alkoxy groups, e.g. a vanadyl trialkoxide VO (OR) ^, a monohalogenated vanadylic oxide VO (OR) gX or a di-halogenated vanadyl monoalkoxide VO (OR) XoJ are generally not just for production suitable for copolymers which have a molecular weight and compound distribution within narrow limits, but they

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also deliver high copolymer yields per unit weight Catalyst.

The use of such compounds containing alkoxy groups as catalysts for polymerization and Interpolymerization of olefins is in Japanese Patents 739 ^ (19.61), 7132 (1963), I379O (I963) and others have been suggested. Of the alcoholic residue in the compounds mentioned however, only has a straight or branched chain aliphatic alkyl group. It is also described there that the active in the polymerization Centers of the catalysts from Ziegler-Natta-Tyρ the transition metal. The effect of one on that Transition metal located, stereometrically bulky group has not been recognized. The inventors of the presently claimed catalysts have now found that a compound in which a stereometrically bulky group is a cyclic Hydrocarbon radical with 5 or more carbon atoms has, e.g. an aliphatic cyclohydrocarbon group, a bridged cyclohydrocarbon group, a spiro compound type hydrocarbon group and the like than the above alkoxy radical described in the azoxy compounds has been introduced represents a previously unknown, new compound and that a catalyst that contains such a vanadium compound as a component, excellent polymerization activity owns. On. this knowledge is based on the present Invention

It has been found that this is a new type of polymerization catalyst effective in general poly-

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merization of an olefin hydrocarbon, especially from. Ethylene, propylene or other ^ -olefins the interpolymerization of ethylene with 00-olefins and in the copolymerization of ethylene or Cx ^ olefins with diene compounds, polyene compounds and the like.

Accordingly, the present invention relates to catalysts for the polymerization of olefin hydrocarbons ^ which essentially consist of (A) a vanadium compound of the general formula

V5.

in which R represents a group containing a cyclic hydrocarbon radical having 5 to 20 carbon atoms, X represents a halogen atom and m-an integer from 1 to is, and off

(B) an organoaluminum compound of the general formula

in which R ^{1 is} a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen or hydrogen atom and η is any number between 1 and 5.

The present invention also relates to catalysts for the polymerization of olefin hydrocarbons materials that essentially consist of one component (A) and a component (B), said component (A) from the reaction product- a Vanadium compound exists that was obtained

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BATH

(a) by reacting a vanadium compound of the general formula

in which R "is an alkyl group having 1 to 5 carbon atoms means X stands for a halogen atom and m is an integer from 1 to 3, with an alcohol of the general formula

RAW,

in which R stands for a group that has a cyclic Contains hydrocarbon radical with 5 to 20 carbon atoms, or

(b) by reacting vanadyl trichloride with an alcohol of the general formula

RAW,

in which R has the meaning given above or

(c) by reacting a vanadium compound of the general formula

VO (OR)

'3'

in which R has the meaning given above, with a carboxylic acid halide of the general formula

R ¹¹ COCl,

in which R ″ has the meaning given above, and said component (B) consists of an organoaluminum compound of the general formula

consists in which R ^{1 has} a hydrocarbon group

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-D-

1 to 20 carbon atoms, X ^{1 is} a halogen or hydrogen atom and η is any number between 1 and 3.

One of the components that are part of the polymerization catalyst according to the invention consists of a vanadium compound of the general formula

^V ° (° ^R > m ^X > m *

In this formula, R represents a group containing a cyclic hydrocarbon residue having 5 to 20 carbon atoms, and it may include, for example, an alicyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro-type hydrocarbon group and the like. Groups suitable for this purpose are, for example, the cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-cyclopentenyl, 2-cyclohexenyl, 2-cycloheptenyl, ^ -Cyclooctenyl-, 2-methylcyelopentyl-, ^ -tert.- Butylcyclohexyl, 4-phenylcyclohexyl,!, ^ - dimethyicyclohexyl, J-methyl-o-isopropylcyclohexyl, cyclopentylmethyl, cyclohexylethyl, cycloheptylethyl, 2,2-dicyclohexylethyl, 2-norbornyl, 5-, bornyl Norbornen-2-yl, 3-pinanyl, cyclopentane-spiro-cyclobutane-3 ¹ -yl, spiro-bicyclohexan - ^ - yl, 2-indenyl, 1-indanyl and the like groups.

As compounds that have such groups are Essentially to name the vanadyl tricyclopentoxide, Vanadyl tricyclohexoxide, vanadyl tri- (5-cyclopentene oxide), Vanadyl-tri- (3-methylcyclohexoxide), vanadyl-tri - (^ - tert-butylcyclohexoxide), Vanadyl trimentoxide,

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Vartadyl-1r ± - (cyclohexylmethoxide), vanadyl-tribornyloxyd, vanadyl-tri- (5-norbornen-2-yloxyd), vanadyltri- (2-indanyloxyd), chlorovanadyl-di-icyclopentoxide), chlorvanadyl-di- (cyclohexoxide), chlorvanadyl-di-O-cyclopentenoxide), chlorvanadyl-di-O-methylcyclohexoxide), chlorvanadyl-di- (5-tert-butylcyelohexoxide), chlorvanadyl-di- (menthoxide), chlorvanadyl-di- (eyclohexylmethoxide) ), Chlorvanadyl-di-Cbornyloxyd), Chlorvanadyl-di- (5-norbornen-2-yloxyd) _t Chlorvanadyl-di- (2-indanyloxyd), Diehlorvanadyl-cyclopentoxide, Dichlorvanadyl-cyclohexoxide, Dichlorvanadyl- (3-cyclopentenoxide) , Dichlorvanadyl- (3-methylcyclohexoxide ) ₃ dichlorvanadyl- (tert-butylcyelohexoxide), dichlorvanadylmethoxide, dichlorvanadyl- (eye1ohexyIraethoxide), dichlorvanadyl-bornyloxyd, diehlor-vanadyl- (2-norbornene-2-dichloro-nadyl), -indanyloxyd) and the like.

These vanadium compounds can be used according to any appropriate methods are produced, for example by the following procedures: (a) A vanadium compound of the general formula

in which R "is an alkyl group having 1 to 5 carbon atoms means, X stands for a halogen atom and η is an integer from 1 to 3 is is made with an alcohol of the general formula

- RAW

implemented, in which R represents a group that a cyclohydrocarbon residue is 5 to 20 Contains carbon atoms.

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(b) Vanadyl trichloride is mixed with an alcohol of the ' general formula - ".

RAW

implemented, in which R has the meaning given above owns. "

(c) A vanadium compound of the general formula

in which R has the meaning given above, with a carboxylic acid halide the general formula

R ¹¹ GOCl,

in which R "has the meaning given above, implemented. ■

The vanadyl trialkoxide compounds referred to in the Description of the invention reference is made, for example, by one of the following working methods become: =

The compound is obtained by bringing about an alcohol exchange reaction between an alcohol (ROH) which contains the mentioned group _y with the cyclic hydrocarbon radical, and vanadyl triethoxide in an inert solvent and then removing the ethanol and the solvent as an azeotropic mixture. The implementation proceeds according to the following scheme:

VO (CC ₂ H ₅ ) + 3 ROH -> VO (OR), + 3 CXOH.

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BATH ORIGINAL

Furthermore, the Halogenvanadylalkoxde can with the help the following reaction are produced: A vanadyl trialkoxide is used, which the group with the cyclic hydrocarbon radical, with acetyl chloride in an inert solvent and then removes the solvent and acetic acid ester from the mixture. The implementation goes as follows:

VO (OR), + (> m) CH ₃ COCl - * V0 (OR) _m Cl ₃ _ _m + -. (3-In) CH ₃ COOR.

In addition, a vanadyl trialkoxide compound can be used or a halovanadyl alkoxide compound by reacting vanadyl trichloride with an alcohol, the contains the group with the cyclic hydrocarbon radical, prepared in an inert solvent will. The implementation proceeds according to the following scheme:

VOX, + m ROH ^ V0 (0R) _m X, _ _m + m HX.

In those cases where two or more groups, which the cyclic hydrocarbon radicals "contained in the vanadium compounds so produced the groups mentioned can of course be identical to or different from one another.

Furthermore, these vanadium compounds do not need individual compounds to be; mixtures of two or more types of the compounds mentioned * and in some cases even the reaction mixtures obtained in the reactions described above as one component of the polymerization catalysts be used.

These reactions can be carried out in the absence of a solvent, but they become convenient carried out in an inert solvent.

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As such solvents, hydrocarbon '. _ Compounds or halogenated hydrocarbon compounds are used with particular advantage.

Such solvents can be, for example, hexane, Heptane, octane, petroleum ether, ligroin, other petroleum fractions, benzene, toluene, xylene, cyclohexane, methylcyclohexane, Methylene dichloride, ethylene dichloride, chlorine benzene and the like can be used.

It is particularly advantageous to use an aromatic hydrocarbon compound such as benzene and the like, because it is well suited for azeotroping with the formed alcohol or ester, for formation contributes to a uniform reaction system and has other advantages. The use of an aliphatic hydrocarbon such as heptane can on the other hand, cause in certain cases the formation of tar-like materials as a by-product. On the other hand, however, the use of an aromatic compound ensures the formation of a uniform Systems.

The other component of the polymerization catalysts of the invention is an organoaluminum compound that of the general formula

is equivalent to. The radical R ¹ in this general formula denotes a radical such as, for example, an alkyl, aryl, aralkyl, alkaryl, cycloalkyl and the like group, and it is particularly advantageous if it is an alkyl group

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represents having 1 to 8 carbon atoms. The radical R ^{1 mentioned} can also be another hydrocarbon group, for example an alkenyl, cyclopentadienylu. Like. Mean group, if necessary.

X 'represents a chlorine, bromine or Jödatom and may, if necessary, a Fluoratöm seinj η is a positive number having a value of "5 or less, preferably 1, 2 1.5T or 3. Suitable representatives of such organoaluminum compounds such as methylaluminum dichloride, fithylaluminiumdichlorid, isobutyl aluminum fithylaluminiumdibromid, Allylaluminiumdichlorid, Vinylaluminiumdiehlorid, ethyl aluminum sesquichloride, methylalulminum, methylaluminum, ÄthyIaIuminiumsesquijodid, Isobutylalurriiniumsesquichlorid, Hexylaluminiumsesquichlorid, diethylaluminum, Diäthylaluminiumbromid, Dipropylaluminiumehlorid, Didodecylaluminiumchlorid, Diäthylaluminiumfluorid, Äthylphenylaluttiiniumchlorid, Trimethylalüminiuni, \ triethylaluminum, Tripropylalumini - .; m, triisobutylaluminum, Trihexylaluininium , Trideeylaluminum, aluminum hydride, mixtures of these compounds, mixtures of the same with halogenated aluminum compounds, such as aluminum chloride, alumin iumbromide and aluminum iodide and the like more.

Among these organoaluminum compounds, one provides Alkyl aluminum halogen compound in the specific case the best results.

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The catalysts of the invention represent a catalyst system which the above-described vanadium verb indungen and organoaluminum compounds as contains the main components, but if necessary further adequate compounds as a third component of the catalysts may contain. As such a third component, for example a compound that acts as an electron donor compound and a coordination compound are listed or a charge transfer complex with the organoaluminum compounds or the Forms vanadium compounds, such as amines, cyclonitrogen compounds, Acid amides, ethers, esters, ketones and aldehydes, a compound of the elements of group Vb of the periodic table, such as phosphorus, arsenic, antimony, bismuth and the like, various chelating agents For this purpose there are also numerous oxidizing compounds available, of which one may assume that they are an excessive reduction in Able to prevent vanadium compounds through the organoaluminum compounds. The halogens, sulfur, metal halides, Oxygen, nitro compounds, nitroso compounds, ■ organic nitrates, nitrites, N-oxide compounds, P-oxide compounds, azo compounds, organic sulfides, Disulfiae, quinones, acid halides and the like are listed will.

The novel polymerization catalysts according to the invention can be used as polymerization catalysts for the polymerization of Olef ^ hydrocarbons, especially von'ätthylen and <X -olefins, for the copolymerization of ethylene with <X-olefins and the

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BATH ORIGINAL

Copolymerization of ethylene with <K olefins and polyene compounds and the like can be used. The c <-olefins which can be used for the homogeneous polymerization mentioned above, the copolymerization with ethylene and the three-component copolymerization correspond to the general formula

CH ₂ = CH.R " V ,,.

in which R "'is a hydrocarbon group with 1 to Represents 20 carbon atoms. As, for example, suitable representatives of the aforementioned <tf-01efine are to be mentioned propylene, butene- (1), pentene- (1), 3-methylbutene- (1), hexene- (1), 3-methylpentene- (1), 4-methylpentene (i), heptene (1), decene (1), vinylcyclopentane and the like. Among them, a low molecular weight alkylene such as propylene, butene- (1) and the like., · used particularly often. ;

A scliwef el-vulcanizable elastomer can through Use of a polyene compound in the production of an amorphous copolymer from ethylene and c <-olefins. are obtained. As suitable for this Polyene compounds include conjugated diene compounds such as isoprene, piperylene, and the like, and also non-conjugated polyene compounds, as above Bridges linked cyclic hydrocarbon compounds, monocyclic compounds, heterocyclic compounds, chain compounds, spiro compounds and the like. As a non-conjugated Polyene compounds are essentially to be cited as examples: dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, cyclooctadiene,

9 Ö 9 8 Ö 6/1 3 4 i BAD

o-methyl- ^ JiS ^ -tetrahydroinden, 1,4-hexadiene, 1,6-octadiene and others more. Especially those aliphatic diene compounds that. are known to have only a low interpolymerizability, can be used well for interpolymerization to be brought.

There is no particular limitation on it d, it ratio in which the in the invention Polymerization catalysts used organoaluminum compounds and vanadium compounds must be related to each other, but one achieves with the application a molar ratio of from 1: 1 to 10,000: 1, preferably from 2: T to 300: 1, are easily excellent Results. As far as the concentration in the reaction medium is concerned, a concentration is often used on the vanadium compounds from 0.01 to 50 millimoles per liter, preferably from 0.1 to 10 millimoles per. Liters, applied. In certain cases one achieves even at lower concentrations of 0.01 millimoles per liter or below, e.g. with those in the On the order of 10 millimoles per liter, an excellent activity. As for the concentration of organoaluminum compounds As far as the reaction system is concerned, a concentration of 0.1 to 100 millimoles per liter, preferably 1 to 20 millimoles, is often used per liter, used.

When the polymerization catalysts according to the invention are used, there is also no special restriction with regard to the order in which they are added

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Catalysts and the monomers, and the addition of the same to the reaction system can be carried out by any procedure. In general, however, one achieves when the catalyst components (A) and (B) are added separately to the polymerization system in the presence of the Monomers have a greater catalytic activity than they can be achieved by using a previously prepared mixture of the catalyst components mentioned are used. With regard to the occurring with the passage of time However, change in catalytic activity may in some cases be better for a product use that has been obtained by previously mixing and reacting the catalyst components.

In those cases where the monomer components, before especially polyene compounds are used, the monomers mentioned can be dissolved beforehand in the reaction medium or they can be added continuously or intermittently together with the other monomers.

The present invention is now intended to be understood by the following Examples are explained in more detail, but in none Way to express a limitation of the invention.

Example 1 .

In a 150 ml four-necked flask equipped with a stirrer, Equipped with thermometer, reflux condenser and dropping funnel and after depressurization was filled with argon, 20.1 g (100 millimoles) of vanadylr Triethoxyd, dissolved in 50 ml of benzene, filled.

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Anschließendwurden 31.2 ml (300 millimoles) of cyclohexanol was added and the whole was refluxed for about 2 hours at a Außentemperäur of 90 to 100 ⁰ C under reflux.

The alcohol formed was from the reaction mixture together with the benzene by azeotropic distillation removed, and the unreacted materials were removed by distillation under reduced pressure.

The reaction product was 25.5 g of Vandyl tricyclohexoxide obtain. This product consists of a yellow, crystalline solid with a melting point M, 5 ° C.

Comparative experiment 1

1 liter of n-heptane was filled into a two-liter flask. A gas mixture of 40 moles of ethylene and 60 moles of propylene was then passed through the flask, which had been placed in a ^{thermostat kept at 30 ° C., at a rate of 10 normal liters per minute in order to} To saturate heptane with it. Then 3 millimoles of ethyl aluminum sesquichloride were added

l (CpHj-) .. ε ^ Ι-ΐ

and 0.3 millimoles of the vanadyl tricyclohexoxide described above added in this order, and then ethylene and propylene were added while stirring. initiated for 30 minutes. To stop the reaction, 30 milliliters of methanol were added. After the reaction mixture was sufficiently washed out with methanol, this reaction mixture was poured into a poured a large amount of methanol in order to

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1936486

To coagulate sat »After, the subsequent drying 28.4 g of a white, amorphous., solid Copolymer obtained.

The intrinsic viscosity number (intrinsic viscosity) of the said interpolymer in a Xyloliösung, at 70 ⁰ C measured was 2.40 dl / g. In addition, the propylene content of the copolymer obtained, as the infrared absorption spectroscopic analysis showed, was 40.8 mol- ^.

Vanadyl trichloride was used instead of vanadyl tricyclohexoxide used, sb only 23.5% of the copolymer was obtained, which proves that the vanadyltricyclohexoxide has a greater polymerization activity than vanadyl trichloride.

Was the polymerization under the same conditions as above, but with the modification carried out using butene- (1) in place of propylene, 16.3 g of one was obtained Mixed polymer.

Example 2

In _; 14.3 g (39.3 millimoles) of vanadyl tricyclohexoxide, dissolved in 23 ml of benzene, were introduced into a 100 millliter four-necked flask which had been equipped with a stirrer, thermometer, reflux condenser and dropping funnel and had been filled with argon after the pressure had been reduced. Thereafter, 2.79 milliliters (39, 'J'Millimol) acetyl -'"-"

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chloride, dissolved in 10 milliliters of benzene, drop by drop gradually added with stirring.

ο, ^Λ

After the completion of the dropwise addition, the Mixture at an outside temperature of 100 C.

Heated under reflux for 1 hour. .

After removing the solvent and the cyclohexyacetate 12 g of monochlorovanadyl dicyclohexoxide were obtained from the reaction mixture by means of distillation obtain. ·

Comparative experiment 2

500 ml of n-heptane were filled into a one-liter flask and kept at a temperature of 25 ° C. Then ethylene at a rate of 1.5 normal liters per minute under ordinary pressure up to Saturation initiated. In addition, 10 millimoles of Ethylaiumi.niumdichlorid and 0.0 ^ 2 millimoles of as Monochlorvanadyl-dicyclohexoxide prepared above was added, and the ethylene was stirred for 1 hour at a rate of 1.5 normal liters forwarded per minute. There were 12.85 g of a white, solid polymer obtained, the one had an intrinsic viscosity of 3 * 77 dl / g.

Comparison attempt 3

JO ml of n-heptane were filled into a 100 ml autoclave and then propylene was fed at 40 ° C. The pressure in the autoclave was kept at 5 kg / cm. Then 3.80 millimoles of triethylaluminum and 1.27 millimoles of the monochlorvanadyl prepared as above were

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BATH

dicyclohexoxydes was added and the reaction was continued with stirring for 3 hours of a white, solid polymer obtained because it had an intrinsic viscosity of 4.47 dl / g.

Example 3

Were 10 g (50 millimoles) of vanadyl triethoxide with 23 * 1 g (150 millimoles) borneol in the same V / eise, as described in Example 1, implemented, then the benzene and the ethanol by azeotropic Distillation removed and the unreacted materials by distillation under reduced Removed pressure, 25.7 g of light yellow, solid vanadyl tribomyl oxide were obtained.

- Example 4

By mixing and reacting a solution of 2.98 g (24 millimoles) 5-hydroxymethyl-2-norbornene in 20 ml of benzene with a solution of 2.08 g (12 millimoles) of vanadyl trichloride in 20 ml of benzene in the presence of argon, a benzene solution of chlorvanadyl dinorbornyl methoxide became manufactured, the concentration of which is 0.3 millimoles / nil fraud.

Comparison attempt 4

A two-liter flask was filled with 1 liter of n-heptane. A gas mixture of 40 mol # ethylene and 60 mol ^ propylene was bubbled through at 15 ° C to saturate the n-heptane.

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After adding 80 millimoles of isoprene and 3 millimoles of ethylaluminum sesquichloride and 0.3 millimoles of monochlorovanadyl dicyclohexoxide, the reaction took 50 minutes continued for a long time with stirring and passage of the gas mixture at the rate indicated above. By working up the reaction mixture in the same way as described in Comparative Experiment 1 is, 16.1 g of a white, solid copolymer were obtained, which has an intrinsic viscosity of 0.85 dl / g, a propylene content of 21.5 mol # and an iodine number of 3 * 6.

When the above reaction is repeated using vanadyl trichloride received instead of monochlorvanadyl dicyclohexoxide one 7 * 83 g of an amorphous copolymer, whose Intrinsic viscosity 1.32 dl / g, its propylene content 35 * 3 mol- $ 6 and its iodine number was 0.9.

From these experiments it is clear that when using the monochloro-vanadyl-dicyclohexoxide the retarding effect on the dienes is reduced and the interpolymerizability is increased.

Comparative experiment 5

1 liter of n-heptane was filled into a two-liter flask, then a gas mixture consisting of 40 mol% ethylene and 60 mol% propylene and hydrogen was introduced at 30 ° C. at rates of 10 normal liters per minute and 2 normal liters per minute, respectively 'to saturate the n-heptane. After adding 10 millimoles

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S-ethylidene - ^ - norbornene, 4 millimoles of ethylaluminum sesquichloride and 0.2 millimoles of vanadyl tricyclahexoxide, the reaction was stirred for 30 minutes and passing the gas mixture and hydrogen at the rates noted above continued. After processing the Reäktiönsge ' Mixing in the manner described in Comparative Experiment 1 was 15.8 g of a white, solid mixed polymer obtained / whose basic molar viscosity ^ number 1.50 dl / g, its propylene content 36.3 Mpl- · ^ and whose iodine number is 19.5 *:

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Claims (1)

Claims Catalysts for the polymerization of olefin hydrocarbons, characterized in that they consist of
(A) a vanadium compound of the general formula in which R denotes a radical which is a cyclic hydrocarbon group having 5 to 20 carbon atoms contains, X represents a halogen atom and m is an integer from 1 to 3 is and (B) an organoaluminum compound of the general formula. ^Α1Β 'η ^χΙ 3-η in which R ^{1 is} a hydrocarbon radical having 1 to 20 carbon atoms, X ^{1 is} a halogen or hydrogen atom and η is a number from 1 to 3. 2. Catalyst according to claim 1, characterized in that said cyclic hydrocarbon radical from consists of a cyclohexyl radical. 3. Catalyst according to claim 2, characterized in that that the vanadium compound from vanadyl tricyclohexoxide consists. 4. Catalyst according to claim 2, characterized in that that the vanadium compound from Monochlorvanadyl-dicyclohexoxyd consists. 909886/1344 ° R'G / WA INSPECTED 5. Catalyst according to claim 1, characterized in that said cyclic hydrocarbon radical consists of a bornyl residue. 6. Catalyst according to claim 5 # characterized in that that the vanadium compound consists of vanadyl tribornyl oxide. 7. Catalyst according to claim l, characterized in that that the mentioned cyclic hydrocarbon radical consists of a norbornyl radical. 8. Catalyst according to claim 7 # characterized in that that the vanadium compound consists of chlorvanadyl dinorbornyl methoxide. 9 «Catalyst according to claim 1, characterized in that component (B) consists of an alkyl aluminum halide consists. 10. Catalyst according to claim 9, characterized in that component (B) consists of an alkylaluminum sesquihalide consists. 11. Catalyst according to claim 9, characterized in that component (B) consists of an alkyl aluminum dihalide -consists. 12. Catalyst according to claim 1, characterized in that that component (B) consists of a trialkylaluminum. 909886 / 13U Catalysts for the polymerization of olefin hydrocarbons, characterized in that they consist of the reaction products of components (A) and (B), wherein (A) represents a vanadium compound that has been produced is either (a) by reacting a vanadium compound of the general formula VO (OR ") _m X _{> m} , · in which R "denotes an alkyl radical having 1 to 5 carbon atoms, X a halogen atom represents and m is an integer from 1 to 3, with an alcohol of the general formula RAW, in which R is a radical containing a cyclic hydrocarbon group having 5 to 20 carbon atoms, or (b) by reacting vanadyl trichloride with an alcohol of the general formula RAW, in which R has the meaning given above, or (c) by reacting a vanadium compound of the general formula VO (OR) ₃ , in which R has the meaning given above, with a carboxylic acid halide the general formula R ¹¹ COCl, 909886/1344 in which R "has the meaning given above, and the component mentioned (B) an organoaluminum compound represented by the general formula ^A1R Wn represents, in the R ^! denotes a hydrocarbon radical having 1 to 20 carbon atoms, X ¹ denotes a halogen or hydrogen atom and η is a number from 1 to 3. 14. Catalyst according to claim 13, characterized in that that component (A) consists of a member of the group of vanadium compounds which according to the Arbeltswelse listed under (a). 15 * catalyst according to claim 13, characterized in that that component (A) consists of a member of the group of vanadium compounds, which have been manufactured according to the method specified under (b). l6. Catalyst according to claim 13, characterized in that that component (A) consists of a member of the group of vanadium compounds which, according to the have been manufactured under (c). 86/1344 ^8AD original